NiO+YSZ anode substrate for screen-printing fabrication of YSZ electrolyte film in solid oxide fuel cell

Anode substrate has a great effect on screen-printing fabrication of yttria-stabilized zirconia (YSZ) electrolyte film and cell performance. In this work, NiO+YSZ anode substrate was prepared by a conventional ceramic sintering method, on which dense YSZ electrolyte film was successfully fabricated by screen-printing method. Microstructure of the anode substrate and cell performance were investigated. The optimal amount of addition of starch to the anode substrate was 20 wt%. The optimal temperature for pre-sintering of NiO powder was 800 °C. A single cell with the NiO powder pre-sintered at 800 °C exhibited the highest power density of 0.95 W cm⁻² at 700 °C.     

Thin porous Ni-YSZ films as anodes for a solid oxide fuel cell

Porous Ni-YSZ (YSZ—yttria-stabilized zirconia) films were fabricated by reactive co-sputtering of a Ni and a Zr-Y target, followed by sequentially annealing in air at 900 °C and in vacuum at 800 °C. The Ni-YSZ films comprised small grains and pores that were tens of nanometers in size. The porous Ni-YSZ films were used as an anode on one side of a YSZ electrolyte disc and a La_0.7Sr_0.3MnO₃ thick film was used as a cathode on the other side of the disc to form solid oxide fuel cells (SOFCs). The voltage-current curves of the SOFCs with single- and a triple-layered porous anodes were measured in a single-chamber configuration, in a mixture of CH₄ and air (CH₄:O₂ volume ratio=2:1). The maximum power density of the SOFC using the single-layered porous Ni-YSZ thin films as the anode was 0.38 mW cm⁻², which was lower than that of 0.76 mW cm⁻², obtained using a screen-printed Ni-YSZ thick anode. The maximum power density of the SOFC with a thin anode was increased, but varied between 0.6 and 1.14 mW cm⁻² when a triple-layered porous Ni-YSZ anode was used.     

Epitaxial growth of YSZ buffer layer for YBa2Cu3O7−δ coated conductor by reel-to-reel pulsed laser deposition

Yttria-stabilized zirconia (YSZ) buffer layers were deposited on CeO₂ buffered biaxially textured Ni-W substrate by reel-to-reel pulsed laser deposition (PLD) for the application of YBa₂Cu₃O_7−δ (YBCO) coated conductor and the influence of substrate temperature and laser energy on their crystallinity and microstructure were studied. YSZ thin films were prepared with substrate temperature ranging from 600 to 800 °C and laser energy ranging from 120 to 350 mJ. X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were used to investigate how thin film structure and surface morphology depend on these parameters. It was found that the YSZ films grown at substrate temperature below 600 °C or laser energy above 300 mJ showed amorphous phase, the (0 0 1) preferred orientation and the crystallinity of the YSZ films were improved with increasing the temperature, but the surface roughness increased simultaneously, the SEM images of YSZ films on CeO₂/NiW tapes showed surface morphologies without micro-cracks. Based on these results, we developed the epitaxial PLD-YSZ buffer layer process at the tape transfer speed of 3-4 m/h by the reel-to-reel system for 100 m class long YBCO tapes.     

Characterization of single-crystalline In2O3 films deposited on Y-stabilized ZrO2 (1 0 0) substrates by MOCVD

Epitaxial In₂O₃ films have been deposited on Y-stabilized ZrO₂ (YSZ) (1 0 0) substrates by metalorganic chemical vapor deposition (MOCVD). The films were deposited at different substrate temperatures (450-750 °C). The film deposited at 650 °C has the best crystalline quality, and observation of the interface area shows a clear cube-on-cube epitaxial relationship of In₂O₃(1 0 0)||YSZ(1 0 0) with In₂O₃[0 0 1]||YSZ[0 0 1]. The Hall mobility of the single-crystalline In₂O₃ film deposited at 650 °C is as high as 66.5 cm² V⁻¹ s⁻¹ with carrier concentration of 1.5 × 10¹⁹ cm⁻³ and resistivity of 6.3 × 10⁻³ Ω cm. The absolute average transmittance of the obtained films in the visible range exceeds 95%.     

Nanostructure of photocatalytic TiO2 films sputtered at temperatures below 200 °C

The article reports on correlations between the process parameters of reactive pulsed dc magnetron sputtering, physical properties and the photocatalytic activity (PCA) of TiO₂ films sputtered at substrate surface temperature T_surf ≤ 180 °C. Films were deposited using a dual magnetron system equipped with Ti (Ø50 mm) targets in Ar + O₂ atmosphere in oxide mode of sputtering. The TiO₂ films with highly photoactive anatase phase were prepared without a post-deposition thermal annealing. The decomposition rate of the acid orange 7 (AO7) solution during the photoactivation of the TiO₂ film with UV light was used for characterization of the film PCA. It was found that (i) the partial pressure of oxygen pO₂ and the total sputtering gas pressure p_T are the key deposition parameters influencing the TiO₂ film phase composition that directly affects its PCA, (ii) the structure of sputtered TiO₂ films varies along the growth direction from the film/substrate interface to the film surface, (iii) ∼500 nm thick anatase TiO₂ films with high PCA were prepared and (iv) the structure of sputtered TiO₂ films is not affected by the substrate surface temperature T_surf when T_surf < 180 °C. The interruption of the sputtering process and deposition in long (tens of minutes) pulses alternating with cooling pauses has no effect on the structure and the PCA of TiO₂ films and results in a decrease of maximum value of T_surf necessary for the creation of nanocrystalline nc-TiO₂ film. It was demonstrated that crystalline TiO₂ films with high PCA can be sputtered at T_surf ≤ 130 °C. Based on obtained results a phase zone model of TiO₂ films was developed.     

Defects in nanocrystalline Nb films: Effect of sputtering temperature

Thin niobium (Nb) films (thickness 350-400 nm) were prepared on (1 0 0)Si substrate in a UHV chamber using the cathode beam sputtering. The sputtering temperature T_s was varied from 40 up to 500 °C and the influence of the sputtering temperature on the microstructure of thin Nb films was investigated. Defect studies of the thin Nb films sputtered at various temperatures were performed by slow positron implantation spectroscopy (SPIS) with measurement of the Doppler broadening of the annihilation line. SPIS was combined with transmission electron microscopy (TEM) and X-ray diffraction (XRD). We have found that the films sputtered at T_s = 40 °C exhibit elongated, column-like nanocrystalline grains. No significant increase of grain size with T_s (up to 500 °C) was observed by TEM. The thin Nb films sputtered at T_s = 40 °C contain a high density of defects. It is demonstrated by shortened positron diffusion length and a high value of the S parameter for Nb layer compared to the well-annealed (defect-free) bulk Nb reference sample. A drastic decrease of defect density was found in the films sputtered at T_s ≥ 300 °C. It is reflected by a significant increase of the positron diffusion length and a decrease of the S parameter for the Nb layer. The defect density in the Nb layer is, however, still substantially higher than in the well-annealed reference bulk Nb sample. Moreover, there is a layer at the interface between the Nb film and the substrate with very high density of defects comparable to that in the films sputtered at T_s < 300 °C. All the Nb films studied exhibit a strong (1 1 0) texture. The films sputtered at T_s < 300 °C are characterized by a compressive macroscopic in-plane stress due to lattice mismatch between the film and the substrate. Relaxation of the in-plane stress was observed in the films sputtered at T_s ≥ 300 °C. The width of the XRD profiles of the films sputtered at T_s ≥ 300 °C is significantly smaller compared to the films sputtered at lower temperatures. This is most probably due to a lower defect density which results in reduced microstrains in the films sputtered at higher temperatures.     

Structural and optical properties of YSZ thin films grown by PLD technique

We report on the structural and optical properties of yttria stabilized zirconia (YSZ) thin films grown by pulsed laser deposition (PLD) technique and in situ crystallized at different substrate temperatures (T_s = 400 °C, 500 °C and 600 °C). Yttria-stabilized zirconia target of ∼1 in. diameter (∼95% density) was fabricated by solid state reaction method for thin film deposition by PLD. The YSZ thin films were grown on an optically polished quartz substrates and the deposition time was 30 min for all the films. XRD analysis shows cubic crystalline phase of YSZ films with preferred orientation along 〈1 1 1〉. The surface roughness was determined by AFM for the films deposited at different substrate temperatures. The nano-sized surface roughness is found to increase with the increase of deposition temperatures. For the optical analysis, a UV-vis-NIR spectrophotometer was used and the optical band gap of ∼5.7 eV was calculated from transmittance curves.     

Electrochemical properties of electrosynthesized TiO2 thin films

Titanium dioxide (TiO₂) thin films prepared by cathodic electrodeposition on indium-tin-oxide coated glass substrates from simple aqueous peroxo-titanium complex solutions have been studied as a function of sintering temperature (25-500 °C). The films crystallized in to anatase phase at relatively low temperature (300 °C). Electrochemical properties of amorphous and anatase films were investigated by cyclic voltammogram (CV) in lithium ion containing organic electrolyte. All the films were found to show reversible electrochemical properties upon Li⁺ ion intercalation. The effects of sintering temperature on the crystallinity and consequently on the electrochemical properties of TiO₂ has been discussed.     

Characterization of YSr2Fe3O8 − δ as electrode materials for SOFC

YSr₂Fe₃O_8 − δ was prepared by traditional solid state reaction method and characterized by X-ray diffraction, ac impedance, dc conductivity, dilatometry and thermogravimetric analysis for possible use in solid oxide fuel cells (SOFCs). YSr₂Fe₃O_8 − δ crystallizes with tetragonal symmetry in the space group P4/mmm and found to be stable at high temperatures under H₂ and air. Four probe dc electrical conductivity measurements show that the conductivity increases up to 745 K and then decreases with temperature; the highest conductivity σ_745K = 43.5 S cm^− 1. The n-type conductivity at low oxygen partial pressure (pO₂) changes to p-type at high pO₂. Polarization behavior was investigated measuring the ac impedance response in symmetrical cell arrangements in air with YSZ and GDC electrolytes. Cathodic area specific resistance (ASR) varies with firing temperature. The lowest area specific resistance was observed with a GDC electrolyte fired at 1000 °C. In case of YSZ, ASR increases and in case of GDC, ASR decreases in air when electrode firing temperature decreases. At 800 °C ASRs are 0.20 Ω cm² and 0.65 Ω cm² with GDC and YSZ electrolytes, respectively, in air. Fuel cell measurements with symmetrical electrodes were performed using a thin YSZ electrolyte under H₂ at anode and air at cathode, show that the power density is about 0.035 W/cm² at 900 °C.     

Electrochemical behaviour of sputtered c-V2O5 and LiCoO2 thin films for solid state lithium microbatteries

Here are reported for the first time electrochemical data on all-solid-state lithium microbatteries using crystalline sputtered V₂O₅ thin films as cathode materials and LiPON as solid electrolyte. The stable specific capacity of 30 µAh/cm² found with a 2.4 µm thick film competes very well with the best values obtained for solid state microbatteries using amorphous films. With the challenge of decreasing the temperature of heat treatment for sputtered LiCoO₂ thin films, we show that a temperature of 500 °C combined with an optimized bias sputtering (-50 V) allows to get highly crystalline deposits, to minimize the presence of Co₃O₄ and to suppress any trace of the cubic phase. At the same time the theoretical specific capacity is reached in the 4.2 V-3 V range and a good cycling behaviour is achieved with a high capacity of 50 µAh/cm²/µm after 140 cycles at 10 µA.cm².     

Annealing effects on structural, optical and electrical properties of e-beam evaporated CuIn0.5Ga0.5Te2 thin films

CuIn_0.5Ga_0.5Te₂ (CIGT) thin films have been prepared by e-beam evaporation from a single crystal powder synthesized by direct reaction of constituent elements in a stoichiometric proportion. Post-depositional annealing has been carried out at 300 and 350 °C. The compositions of the films were determined by energy dispersive X-ray analysis (EDXA) and it was found that there was a remarkable fluctuation in atomic percentage of the constituent elements following to the post-depositional annealing. X-ray diffraction analysis (XRD) has shown that as-grown films were amorphous in nature and turned into polycrystalline structure following to the annealing at 300 °C. The main peaks of CuIn_0.5Ga_0.5Te₂ and some minor peaks belonged to a binary phase Cu₂Te appeared after annealing at 300 °C, whereas for the films annealed at 350 °C single phase of the CuIn_0.5Ga_0.5Te₂ chalcopyrite structure was observed with the preferred orientation along the (1 1 2) plane. The effect of annealing on and near surface regions has been studied using X-ray photoelectron spectroscopy (XPS). The results indicated that there was a considerable variation in surface composition following to the annealing process. The transmission and reflection measurements have been carried out in the wavelength range of 200-1100 nm. The absorption coefficients of the films were found to be in the order of 10⁴ cm⁻¹ and optical band gaps were determined as 1.39, 1.43 and 1.47 eV for as-grown and films annealed at 300 and 350 °C, respectively. The temperature dependent conductivity and photoconductivity measurements have been performed in the temperature range of −73 to 157 °C and the room temperature resistivities were found to be around 3.4 × 10⁷ and 9.6 × 10⁶ (Ω cm) for the as-grown and annealed films at 350 °C, respectively.     

Spray pyrolysis deposition of YSZ and YSZ-Pt composite films

In the present paper procedures are described for spray pyrolysis deposition of YSZ films (0.1-30 μm in thickness) with 8 or 15 mole % of YO_1.5 on different substrates. Aqueous or ethylene glycol solutions of Y-Zr-citrates were used as starting material and O₂ as carrier gas. The crystal structure and the morphology of the films were studied.The optimal deposition and post-deposition annealing conditions were defined, taking into account the desired film thickness and characteristics. Substrate temperatures of 250 °C during the deposition followed by heating for 10 min to 400 °C after every spraying and to 590 °C after every three sprayings with final annealing at 590 °C for 2 h in static air atmosphere were found to be suitable for the production of dense, uniform and cracks-free films.     

Surface morphology and luminescence characterization of β-FeSi2 thin films prepared by pulsed laser deposition

β-FeSi₂ thin films were prepared on Si (1 1 1) substrates by pulsed laser deposition (PLD) with a sintering FeSi₂ target and an electrolytic Fe target. The thin films without micron-size droplets were prepared using the electrolytic Fe target; however, the surface without droplets was remarkably rougher using the Fe target than using the FeSi₂ target. After deposition at 600 °C and then annealing at 900 °C for 20 h, XRD indicated that the thin film prepared using the Fe target had a poly-axis-orientation, but that prepared using the FeSi₂ target had a one-axis-orientation. The PL spectra of the thin films prepared using the FeSi₂ and Fe targets at a growth temperature of 600 °C and subsequently annealed at 900 °C for 20 h had A-, B- and C-bands. Moreover, it was found that the main peak at 0.808 eV (A-band) in the PL spectrum of the thin films prepared using the FeSi₂ target was the intrinsic luminescence of β-FeSi₂ from the dependence of PL peak energy on temperature and excitation power density.     

An analysis of Y2O3:Eu thin films for thermographic phosphor applications

A comparative study of the luminescent properties of Y₂O₃:Eu³⁺ phosphor powders and thin films sputtered from targets prepared from combustion synthesized powders is reported. Thin films of (Y_0.96Eu_0.04)₂O₃ were deposited on silicon substrates. Films deposited at 600 °C had both monoclinic and cubic phases of Y₂O₃, which developed to an oriented cubic phase after annealing. Films and powders showed a linear dependence of the intensity of the ⁵D₇→⁷F₂ (611 nm) transition with temperature in the range 26-660 °C with an average rate of change of 1.8×10⁻⁴ °C⁻¹. The rate of change appears to be dependent on the Eu³⁺ concentration. This work shows that these thin films can be used as thermographic phosphors for remote temperature measurements.     

The luminescence and optoelectrical properties of ITO films prepared by a sputter type negative metal ion deposition

Transparent conducting indium tin oxide (ITO) thin films were prepared on glass substrates by a magnetron sputter type negative ion source which requires cesium (Cs) vapor injection for surface negative ionization on the ITO target surface. Although the film was prepared at 70 °C, it attained high optical transmittance, 88% and low resistivity, 2.03 × 10⁻⁴ Ω cm, at an optimized Cs partial pressure of P_Cs = 1.7 × 10⁻³ Pa. The as-deposited ITO films have a poly-crystalline structure with (2 1 1), (2 2 2), (4 0 0), (4 1 1) and (4 4 0) reflections.Also, ITO films prepared at P_Cs = 1.7 × 10⁻³ Pa were post-deposition vacuum annealed at 300 °C for 30 min. The films had a resistivity of 1.8 × 10⁻⁴ Ω cm and a transparency of 89.2%. The post-deposition vacuum annealed ITO film was used as an anode for a transparent organic light emitting diode (TOLED). A maximum luminance of 19,000 cd/m² was obtained.     

SiO2 film electret with high surface potential stability

The plasma surface treatment and ion implantation were utilized to improve the stability of charge storage in the SiO₂ film electret. It was found that the SiO₂ films treated by argon plasma with the arcing at 700 V for 15 min, or implanted by 150 keV (kilo electron volt) Ar⁺ with a dose of 2 × 10¹¹ cm⁻², after being negatively charged, showed a remnant negative potential as large as 90% of the primary value after being stored in a glass container with desiccant for 10 days. It was also found that after being negatively charged at room temperature and aged at 200-350 °C for several times, the SiO₂ films implanted by 150 keV Ar⁺ had a relatively high remnant potential and it did not decay significantly even after being heated at the aging temperature of 200-350 °C in room atmosphere for 60 min.     

Fabrication of solid oxide fuel cell based on doped ceria electrolyte by one-step sintering at 800 °C

Ce_0.8Gd_0.05Y_0.15O_1.9 (GYDC) electrolyte was prepared by a carbonate co-precipitation method. Lithium nitrate at 1, 1.5, 2 and 3 mol% was added to GYDC as sintering additive. 96% relative density was achieved for GYDC at sintering temperature of 800 °C with addition of 1.5 mol% LiNO₃. The conductivities of GYDC with sintering aids LiNO₃ were measured by a.c. impedance spectroscopy and showed comparable values to that of pure GYDC sample sintered at 1400 °C. A single cell with 1.5 mol% LiNO₃ infiltrated GYDC electrolyte was fabricated by sintering at 800 °C for only 2 h. Lithiated NiO was synthesized by the glycine-nitrate combustion method and employed as cathode material. The cell was tested at temperatures from 500 to 575 °C and a maximum power density of 73 mW cm^− 2 was obtained at 575 °C. These preliminary results indicate that LiNO₃ is a very effective sintering additive for intermediate temperature solid oxide fuel cell fabrication.     

Effects of Ag addition on phase transformation and resistivity of TiSi2 thin films

In this study, the effects of adding Ag to TiSi₂ thin films are examined. It is demonstrated that both the C49 → C54 transformation temperature and the electric resistivity are appreciably lowered with Ag addition. Due to the presence of Ag nanocrystals precipitated at the C49 grain boundaries, the overall grain boundary density would increase to result in the higher nucleation rate of C54 and the lower transformation temperature. The precipitation of pure Ag network can provide another electric current conductive path except for the TiSi₂ grains. Due to the lower vacuum condition and the higher oxygen content in the current sputtered and annealed films, the C49 → C54 transformation temperature and the resistivity of the TiSi₂-20 at%Ag films can only be reduced by ∼100 °C and 10 μΩ cm, as compared with the non-Ag additive films. With better fabrication vacuum, the transformation temperature and resistivity might be lowered to a level below 700 °C and 15 μΩ cm, which are highly applausive for engineering applications.     

Synthesis and characterization of a nano-scaled barium cerate perovskite powder using starch as polymerization agent

The preparation of nano-sized BaCeO₃ powder using starch as a polymerization agent is described herein. Phase evolution during the decomposition process of a (BaCe)-gel was monitored by XRD. A phase-pure nano-sized BaCeO₃ powder was obtained after calcining of the (BaCe)-gel at 920 °C. The resulting powder has a specific surface area of 15.4 m²/g. TEM investigations reveal particles mainly in the size range of 30 to 65 nm. The shrinkage and sintering behavior of resulting powder compacts were studied in comparison to a coarse-grained mixed-oxide BaCeO₃ powder (S_BET = 2.1 m²/g). Dilatometric measurements show that the beginning of shrinkage of compacts from the nano-sized powder is downshifted by 300 °C compared to mixed-oxide powder. Compacts from the nano-sized powder reach a relative density of 91% after sintering at 1450 °C for 10 h.     

Electrochemical properties of nanostructured lanthanum strontium manganite cathode fabricated by electrostatic spray deposition

Electrostatic spray deposition was applied to prepare nanoporous lanthanum strontium manganite (LSM) films with high specific surface area (37.34 m²/g) for the cathode application in solid oxide fuel cell (SOFC). The electrochemical characteristics were investigated at a temperature range from 546 to 777 °C and oxygen partial pressure from 0.01 to 1.0 atm. The diffusion of atomic oxygen and oxygen ion transfer from three-phase boundary to the YSZ electrolyte were found to be the rate-determining steps for oxygen reduction reaction on LSM cathode. The polarization resistance of the LSM prepared using electrostatic spray deposition decreased from 15 to 1.2 Ωcm² with increasing temperature from 546 to 777 °C and the activation energy was 0.81 eV. It was demonstrated that the ESD method offers a promising approach for the preparation of electrochemically active nanoporous layers, particularly applicable for solid oxide fuel cells.